Certain oximinyl allophanates and their use as herbicides

ABSTRACT

Disclosed are novel compounds of the formula ##STR1## in which when R 1  and R 2  are taken separately, R 1  is selected independently from the group consisting of hydrogen and C 1  -C 7  alkyl and R 2  is selected independently from the group consisting of C 1  -C 7  alkyl, phenyl and 2-furanyl, and, when taken together with the carbon atom to which they are attached R 1  and R 2  form a C 3  -C 8  cycloalkyl group; R 3  is selected from the group consisting of C 1  -C 7  alkyl, allyl, phenyl, 3-halophenyl and 3,4-dihalophenyl; and R 4  is selected from the group consisting of C 1  -C 7  alkyl, allyl, cyclohexyl, phenyl, halophenyl, tolyl, anisolyl, nitrophenyl, 3,4-dihalophenyl, 1-naphthyl, p-toluene sulfonyl, trihalomethylphenyl and 2,6-dinitro-4-trihalomethylphenyl. These compounds have herbicidal activity.

The application is a division of the application, Ser. No. 350,218,filed Apr. 11, 1973, on which U.S. Pat. No. 3,957,867 was granted.

This invention is in the chemical arts. It relates to that part oforganic chemistry having to do with allophanates. It also relates toherbicides.

The allophanates of this invention are oximinyl allophanates. They arerepresented by the general structural formula: ##STR2## in which when R¹and R² are taken separately, R¹ is selected independently from the groupconsisting of hydrogen and C₁ -C₇ alkyl and R² is selected independentlyfrom the group consisting of C₁ -C₇ alkyl, phenyl and 2-furanyl, and,when taken together with the carbon atom to which they are attached R¹and R² form a C₃ -C₈ cycloalkyl group; R³ is selected from the groupconsisting of C₁ -C₇ alkyl, allyl, phenyl, 3-halophenyl and3,4-dihalophenyl; and R⁴ is selected from the group consisting of C₁ -C₇alkyl, allyl, cyclohexyl, phenyl, halophenyl, tolyl, anisolyl,nitrophenyl, 3,4-dihalophenyl, 1-naphthyl, p-toluenesulfonyl,trihalomethylphenyl and 2,6-dinitro-4-trihalomethylphenyl. Examples ofC₁ -C₇ alkyl include methyl, ethyl, propyl, isopropyl, butyl, sec.butyl, t-butyl and the like. Examples of C₃ -C₈ cycloalkyl includecyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like. Examplesof specific compounds of this invention include:

Isobutyraldoximinyl-2-methyl-4-ethyl allophanate

Isobutyraldoximinyl-2-methyl-4-(t-butyl) allophanate

Isobutyraldoximinyl-2-methyl-4-(3,4-dichlorophenyl)allophanate

Isobutyraldoximinyl-2-methyl-4-(1-naphthyl)allophanate

Isobutyraldoximinyl-2-(n-propyl-4-methyl allophanate

Isobutyraldoximinyl-2,4-di(n-propyl)allophanate

Isobutyraldoximinyl-2-(n-propyl)-4-(t-butyl)allophanate

Isobutyraldoximinyl-2-(n-propyl)-4-phenyl allophanate

Isobutyraldoximinyl-2-(n-propyl)-4-(3,4-dichlorophenyl)allophanate

Isobutyraldoximinyl-2-(n-propyl)-4-naphthyl)allophanate

Isobutyraldoximinyl-2-phenyl-4-methyl allophanate

Isobutyraldoximinyl-2-phenyl-4-allyl allophanate

Isobutyraldoximinyl-2-phenyl-4-(n-butyl)allophanate

Isobutyraldoximinyl-2,4-diphenyl allophanate

Isobutyraldoximinyl-2-phenyl-4-(p-chlorophenyl)allophanate

Isobutyraldoximinyl-2-phenyl-4-(3,4-dichlorophenyl)allophanate

Isobutyraldoximinyl-2-(3,4-dichlorophenyl)-4-isopropyl allophanate

Isobutyraldoximinyl-2-(3,4-dichlorophenyl)-4-(n-butyl)allophanate

Isobutyraldoximinyl-2-(3,4-dichlorophenyl)-4-phenyl allophanate

Isobutyraldoximinyl-2-(3,4-dichlorophenyl)-4-(p-chlorophenyl)allophanate

Isobutyraldoximinyl-2-(3,4-dichlorophenyl)-4-(m-tolyl)allophanate

Benzaldoximinyl-2-methyl-4-ethyl allophanate

Benzaldoximinyl-2-methyl-4-allyl allophanate

Benzaldoximinyl-2-methyl-4-(n-butyl)allophanate

Benzaldoximinyl-2-methyl-4-phenyl allophanate

Benzaldoximinyl-2-methyl-4-(3-chlorophenyl)allophanate

Benzaldoximinyl-2-methyl-4-(4-chlorophenyl)allophanate

Benzaldoximinyl-2-allyl-4-methyl allophanate

Benzaldoximinyl-2,4-diallyl allophanate

Benzaldoximinyl-2-allyl-4-(n-butyl)allophanate

Benzaldoximinyl-2-allyl-4-isopropyl allophanate

Benzaldoximinyl-2-allyl-4-phenyl allophanate

Benzaldoximinyl-2-allyl-4-(3-chlorophenyl)allophanate

Benzaldoximinyl-2-allyl-4-(4-chlorophenyl)allophanate

Benzaldoximinyl-2-allyl-4-(3,4-dichlorophenyl)allophanate

Benzaldoximinyl-2-allyl-4-(4-methoxyphenyl)allophanate

Benzaldoximinyl-2-allyl-4-(p-toluenesulfonyl)allophanate

Benzaldoximinyl-2-phenyl-4-methyl allophanate

Benzaldoximinyl-2-phenyl-4-ethyl allophanate

Benzaldoximinyl-2-phenyl-4-allyl allophanate

Benzaldoximinyl-2-phenyl-4-(n-propyl)allophanate

Benzaldoximinyl-2-phenyl-4-(n-butyl)allophanate

Benzaldoximinyl-2,4-diphenyl allophanate

Benzaldoximinyl-2-phenyl-4-(3-chlorophenyl)allophanate

Benzaldoximinyl-2-phenyl-4-(4-chlorophenyl)allophanate

Benzaldoximinyl-2-phenyl-4-(3,4-dichlorophenyl)allophanate

Benzaldoximinyl-2-(3-chlorophenyl)-4-methyl allophanate

Benzaldoximinyl-2-(3-chlorophenyl)-4-ethyl allophanate

Benzaldoximinyl-2-(3-chlorophenyl)-4-allyl allophanate

Benzaldoximinyl-2-(3-chlorophenyl)-4-(n-butyl)allophanate

Benzaldoximinyl-2-(3-chlorophenyl)-4-phenyl allophanate

Benzaldoximinyl-2,4-di-(3-chlorophenyl)allophanate

Benzaldoximinyl-2-(3-chlorophenyl)-4-(4-chlorophenyl)allophanate

Benzaldoximinyl-2-(3-chlorophenyl)-4-(3,4-dichlorophenyl)allophanate

Benzaldoximinyl-2-(3-chlorophenyl)-4-(nitrophenyl)allophanate

Benzaldoximinyl-2-(3,4-dichlorophenyl)-4-methyl allophanate

Benzaldoximinyl-2,4-di-(3,4-dichlorophenyl)allophanate

2-(Furaldoximinyl-2,4-dimethyl allophanate

2-Furaldoximinyl-2-methyl-4-ethyl allophanate

2-Furaldoximinyl-2-methyl-4-allyl allophanate

2-Furaldoximinyl-2-methyl-4-(n-propyl)allophanate

2-Furaldoximinyl-2-methyl-4-(n-butyl)allophanate

2-Furaldoximinyl-2-methyl-4-phenyl allophanate

2-Furaldoximinyl-2-methyl-4-(3-chlorophenyl)allophanate

2-Furaldoximinyl-2-methyl-4-(4-chlorophenyl)allophanate

2-Furaldoximinyl-2-methyl-4-(4-methoxyphenyl)allophanate

2-Furaldoximinyl-2-methyl-4-(4-methylphenyl)allophanate

2-Furaldoximinyl-2-phenyl-4-ethyl allophanate

2-Furaldoximinyl-2-phenyl-4-allyl allophanate

2-Furaldoximinyl-2,4-diphenyl allophanate

2-Furaldoximinyl-2-phenyl-4-(3-chlorophenyl)allophanate

2-Furaldoximinyl-2-phenyl-4-(4-chlorophenyl)allophanate

2-Furaldoximinyl-2-(3-chlorophenyl)-4-methyl allophanate

2-Furaldoximinyl-2-(3-chlorophenyl)-4-ethyl allophanate

2-Furaldoximinyl-2-(3-chlorophenyl)-4-allyl allophanate

2-Furaldoximinyl-2-(3-chlorophenyl)-4-phenyl allophanate

2-Furaldoximinyl-2,4-bis-(3-chlorophenyl)allophanate

2-Furaldoximinyl-2-(3-chlorophenyl)-4-(4-chlorophenyl)allophanate

Acetone oximinyl-2,4-dimethyl allophanate

Acetone oximinyl-2-methyl-4-allyl allophanate

Acetone oximinyl-2-methyl-4-phenyl allophanate

Acetone oximinyl-2-methyl-4-(3-chlorophenyl)allophanate

Acetone oximinyl-2-methyl-4-(4-chlorophenyl)allophanate

Acetone oximinyl-2-methyl-4-(3,4-dichlorophenyl)allophanate

Acetone oximinyl-2-methyl-4-(4-methoxyphenyl)allophanate

Acetone oximinyl-2-methyl-4-(nitrophenyl)allophanate

Acetone oximinyl-2-methyl-4-(3-trifluoromethylphenyl)allophanate

Acetone oximinyl-2-allyl-4-methyl allophanate

Acetone oximinyl-2,4-diallyl allophanate

Acetone oximinyl-2-allyl-4-cyclohexyl allophanate

Acetone oximinyl-2-allyl-4-(n-butyl)allophanate

Acetone oximinyl-2-allyl-4-phenyl allophanate

Acetone oximinyl-2-allyl-4-(3-chlorophenyl)allophanate

Acetone oximinyl-2-allyl-4-(3,4-dichlorophenyl)allophanate

Acetone oximinyl-2-allyl-4-(toluenesulfonyl)allophanate

Acetone oximinyl-2-phenyl-4-methyl allophanate

Acetone oximinyl-2-phenyl-4-allyl allophanate

Acetone oximinyl-2-phenyl-4-isopropyl allophanate

Acetone oximinyl-2-phenyl-4-(n-butyl)allophanate

Acetone oximinyl-2,4-diphenyl allophanate

Acetone oximinyl-2-phenyl-4-(3-chlorophenyl)allophanate

Acetone oximinyl-2-phenyl-4-(3,4-dichlorophenyl)allophanate

Acetone oximinyl-2-(3-chlorophenyl)-4-methyl allophanate

Acetone oximinyl-2-(3-chlorophenyl)-4-allyl allophanate

Acetone oximinyl-2-(3-chlorophenyl)-4-(n-butyl)allophanate

Acetone oximinyl-2-(3-chlorophenyl)-4-phenyl allophanate

Acetone oximinyl-di-2,4-(3-chlorophenyl)allophanate

Acetone oximinyl-2-(3-chlorophenyl)-4-(3,4-dichlorophenyl)allophanate

Acetone oximinyl-2-(3-chlorophenyl)-4-(p-toluenesulfonyl)allophanate

Acetone oximinyl-2-(3,4-dichlorophenyl)-4-methyl allophanate

Acetone oximinyl-2,4-di-(3,4-dichlorophenyl)allophanate

2-Butanone oximinyl-2,4-dimethyl allophanate

2-Butanone oximinyl-2-methyl-4-ethyl allophanate

2-Butanone oximinyl-2-methyl-4-allyl allophanate

2-Butanone oximinyl-2-methyl-4-(n-butyl)allophanate

2-Butanone oximinyl-2-methyl-4-phenyl allophanate

2-Butanone oximinyl-2-methyl-4-(m-chlorophenyl)allophanate

2-Butanone oximinyl-2-methyl-4-(3,4-dichlorophenyl)allophanate

2-Butanone oximinyl-2-methyl-4-(o-tolyl)allophanate

2-Butanone oximinyl-2-methyl-4-(m-tolyl)allophanate

2-Butanone oximinyl-2-methyl-4-(p-tolyl)allophanate

2-Butanone oximinyl-2-methyl-4-(1-naphthyl)allophanate

2-Butanone oximinyl-2-methyl-4-(3-trifluoromethylphenyl)allophanate

2-Butanone oximinyl-2-(n-butyl)-4-methyl allophanate

2-Butanone oximinyl-2-(n-butyl)-4-allyl allophanate

2-Butanone oximinyl-2-(n-butyl)-4-ethyl allophanate

2-Butanone oximinyl-2-(n-butyl)-4-isopropyl allophanate

2-Butanone oximinyl-2,4-di-(n-butyl)allophanate

2-Butanone oximinyl-2-(n-butyl)-4-phenyl allophanate

2-Butanone oximinyl-2-(n-butyl)-4-(m-chlorophenyl)allophanate

2-Butanone oximinyl-2-(n-butyl)-4-(3,4-dichlorophenyl)allophanate

2-Butanone oximinyl-2-(n-butyl)-4-(m-tolyl)allophanate

2-Butanone oximinyl-2-(n-butyl)-4-(1- naphthyl)allophanate

2-Butanone oximinyl-2-phenyl-4-methyl allophanate

2-Butanone oximinyl-2-phenyl-4-ethyl allophanate

2-Butanone oximinyl-2-phenyl-4-allyl allophanate

2-Butanone oximinyl-2-phenyl-4-isopropyl allophanate

2-Butanone oximinyl-2-phenyl-4-(n-butyl)allophanate

2-Butanone oximinyl-2,4-diphenyl allophanate

2-Butanone oximinyl-2-phenyl-4-(m-chlorophenyl)allophanate

2-Butanone oximinyl-2-phenyl-4-(p-tolyl)allophanate

2-Butanone oximinyl-2-phenyl-4-(1-naphthyl)allophanate

2-Butanone oximinyl-2-phenyl-4-(3,4-dichlorophenyl)allophanate

2-Butanone oximinyl-2-(m-chlorophenyl)-4-methyl allophanate

2-Butanone oximinyl-2-(m-chlorophenyl)-4-(n-butyl)allophanate

2-Butanone oximinyl-2-(m-chlorophenyl)-4-ethyl allophanate

2-Butanone oximinyl-2-(m-chlorophenyl)-4-phenyl allophanate

2-Butanone oximinyl-2,4-di-(m-chlorophenyl)allophanate

2-Butanone oximinyl-2-(m-chlorophenyl)-4-isopropyl allophanate

2-Butanone oximinyl-2-(m-chlorophenyl)-4-(o-tolyl)allophanate

2-Butanone oximinyl-2-(m-chlorophenyl)-4-(1-naphthyl)allophanate

2-Butanone oximinyl-2-(m-chlorophenyl)-4-(t-butyl)allophanate

2-Butanone oximinyl-2-(m-chlorophenyl)-4-(3,4-dichlorophenyl)allophanate

2-Butanone oximinyl-2,4-di(3,4-dichlorophenyl)allophanate

2-Butanone oximinyl-2-(3,4-dichlorophenyl)-4-methyl allophanate

Methyl isobutylketoximinyl-2,4-dimethyl allophanate

Methyl isobutylketoximinyl-2-methyl-4-isopropyl allophanate

Methyl isobutylketoximinyl-2-methyl-4-(n-butyl)allophanate

Methyl isobutylketoximinyl-2-methyl-4-phenyl allophanate

Methyl isobutylketoximinyl-2-methyl-4-(p-chlorophenyl)allophanate

Methyl isobutylketoximinyl-2-methyl-4-(3,4-dichlorophenyl)allophanate

Methyl isobutylketoximinyl-2-methyl-4-(1-naphthyl)allophanate

Methyl isobutylketoximinyl-2-(n-propyl)-4-methyl allophanate

Methyl isobutylketoximinyl-2-(n-propyl)-4-isopropyl allophanate

Methyl isobutylketoximinyl-2-(n-propyl)-4-(n-butyl)allophanate

Methyl isobutylketoximinyl-2-(n-propyl)-4-phenyl allophanate

Methyl isobutylketoximinyl-2-(n-propyl)-4-(p-chlorophenyl)allophanate

Methyl isobutylketoximinyl-2-(n-propyl)-4-(3,4-dichlorophenyl)allophanate

Methyl isobutylketoximinyl-2-(n-propyl)-4-(1-naphthyl)allophanate

Methyl isobutylketoximinyl-2-phenyl-4-methyl allophanate

Methyl isobutylketoximinyl-2-phenyl-4-isopropyl allophanate

Methyl isobutylketoximinyl-2-phenyl-4-(n-butyl)allophanate

Methyl isobutylketoximinyl-2-phenyl-4-phenyl allophanate

Methyl isobutylketoximinyl-2-phenyl-4-(p-chlorophenyl)allophanate

Methyl isobutylketoximinyl-2-phenyl-4-(1-naphthyl)allophanate

Methyl isobutylketoximinyl-2-phenyl-4-(3,4-dichlorophenyl)allophanate

Methyl isobutylketoximinyl (3,4-dichlorophenyl)-4-methyl allophanate

Methyl isobutylketoximinyl (3,4-dichlorophenyl)-4-isopropyl allophanate

Methyl isobutylketoximinyl (3,4-dichlorophenyl)-4-(n-butyl) allophanate

Methyl isobutylketoximinyl (3,4-dichlorophenyl)-4-phenyl allophanate

Methyl isobutylketoximinyl (3,4-dichlorophenyl)-4-(p-chlorophenyl)allophanate

Methyl isobutylketoximinyl (3,4-dichlorophenyl)-4-(1-naphthyl)allophanate

Acetophenone oximinyl-2,4-dimethyl allophanate

Acetophenone oximinyl-2-methyl-4-ethyl allophanate

Acetophenone oximinyl-2-methyl-4-allyl allophanate

Acetophenone oximinyl-2-methyl-4-isopropyl allophanate

Acetophenone oximinyl-2-methyl-4-(n-butyl)allophanate

Acetophenone oximinyl-2-methyl-4-phenyl allophanate

Acetophenone oximinyl-2-methyl-4-(3,4-dichlorophenyl)allophanate

Acetophenone oximinyl-2-methyl-4-(m-tolyl)allophanate

Acetophenone oximinyl-2-methyl-4-(1-naphthyl) allophanate

Acetophenone oximinyl-2-methyl-4-(3-trifluromethylphenyl)allophanate

Acetophenone oximinyl-2-(n-butyl)-4-methyl allophanate

Acetophenone oximinyl-2-(n-butyl)-4-ethyl allophanate

Acetophenone oximinyl-2-(n-butyl)-4-allyl allophanate

Acetophenone oximinyl-2-(n-butyl)-4-isopropyl allophanate

Acetophenone oximinyl-2,4-di-(n-butyl)allophanate

Acetophenone oximinyl-2-(n-butyl)-4-phenyl allophanate

Acetophenone oximinyl-2-(n-butyl)-4-(3,4-dichlorophenyl)allophanate

Acetophenone oximinyl-2-(n-butyl)-4-(m-chlorophenyl)allophanate

Acetophenone oximinyl-2-(n-butyl)-4-(m-tolyl)allophanate

Acetophenone oximinyl-2-(n-butyl)-4-(1-naphthyl)allophanate

Acetophenone oximinyl-2-phenyl-4-methyl allophanate

Acetophenone oximinyl-2-phenyl-4-ethyl allophanate

Acetophenone oximinyl-2-phenyl-4-allyl allophanate

Acetophenone oximinyl-2-phenyl-4-isopropyl allophanate

Acetophenone oximinyl-2-phenyl-4-(n-butyl)allophanate

Acetophenone oximinyl-2,4-diphenyl allophanate

Acetophenone oximinyl-2-phenyl-4-(m-chlorophenyl)allophanate

Acetophenone oximinyl-2-phenyl-4-(3,4-dichlorophenyl)allophanate

Acetophenone oximinyl-2-phenyl-4-(m-tolyl)allophanate

Acetophenone oximinyl-2-phenyl-4-(1-naphthyl)allophanate

Acetophenone oximinyl-2-(m-chlorophenyl)-4-methyl allophanate

Acetophenone oximinyl-2-(m-chlorophenyl)-4-ethyl allophanate

Acetophenone oximinyl-2-(m-chlorophenyl)-4-allyl allophanate

Acetophenone oximinyl-2-(m-chlorophenyl)-4-(n-propyl)allophanate

Acetophenone oximinyl-2-(m-chlorophenyl)-4-(n-butyl)allophanate

Acetophenone oximinyl-2-(m-chlorophenyl)-4-(m-tolyl)allophanate

Acetophenone oximinyl-2-(m-chlorophenyl)-4-(1-naphthyl)allophanate

Acetophenone oximinyl-2-(3,4-dichlorophenyl)-4-methyl allophanate

Acetophenone oximinyl-2,4-di-(3,4-dichlorophenyl)allophanate

Cyclohexanone oximinyl-2,4-dimethyl allophanate

Cyclohexanone oximinyl-2-methyl-4-ethyl allophanate

Cyclohexanone oximinyl-2-methyl-4-allyl allophanate

Cyclohexanone oximinyl-2-methyl-4-(n-propyl)allophanate

Cyclohexanone oximinyl-2-methyl-4-(n-butyl)allophanate

Cyclohexanone oximinyl-2-methyl-4-phenyl allophanate

Cyclohexanone oximinyl-2-methyl-4-(4-chlorophenyl)allophanate

Cyclohexanone oximinyl -2-methyl-4-(3-chlorophenyl)allophanate

Cyclohexanone oximinyl-2-methyl-4-(4-methoxyphenyl)allophanate

cyclohexanone oximinyl-2-phenyl-4-methyl allophanate

Cyclohexanone oximinyl-2-phenyl-4-allyl allophanate

Cyclohexanone oximinyl-2-phenyl-4-isopropyl allophanate

Cyclohexanone oximinyl-2-phenyl-4-(n-butyl)allophanate

Cyclohexanone oximinyl-2,4-diphenyl allophanate

Cyclohexanone oximinyl-2-phenyl-4-(3-chlorophenyl)allophanate

Cyclohexanone oximinyl-2-phenyl-4-(3-chlorophenyl)allophanate

Cyclohexanone oximinyl-2-phenyl-4-(3,4-dichlorophenyl)allophanate

Cyclohexanone oximinyl-2-phenyl-4-(o-tolyl)allophanate

Cyclohexanone oximinyl-2-phenyl-4-(3-methoxyphenyl)allophanate

Cyclohexanone oximinyl-2-phenyl-4-(3-nitrophenyl)allophanate

Each oximinyl allophanate of this invention is made by reacting anoximinyl carbamate of the formula ##STR3## with an isocyanate of theformula R⁴ N=C=O. Reaction is effected with a catalyst such as, forexample, lead naphthenate, cobalt naphthenate, and the like. Preferably,the reaction is effected in an inert liquid reaction medium such as, forexample, benzene, dioxane, acetonitrile, acetone, dimethylformamide andother inert solvents. The reaction temperature is from about 25° C. toabout 110° C., preferably in the range of from about 55° C. to about100° C.

The precurser oxime carbamate for the oximinyl allophanates of thisinvention is made by carbamoylating an oxime of the formula ##STR4##with an isocyanate of the formula R³ N=C=O in the presence of a basiccatalyst such as, for example, triethylamine.

Each oximinyl allophanate of this invention is also made by reacting aurea compound with phosgene to produce an allophanyl chloride and thendisplacing the labile chloride of the allophanyl chloride by reactionwith an oxime. The reactions are represented by the following equations:##STR5## The initial step of the reaction, i.e., the reaction of theurea compound with phosgene, preferably is carried out at atmosphericpressure in an inert liquid reaction medium such as, for example,benzene. No catalyst is necessary. The reaction temperature is in therange of from about 0° C. to about 100° C.

The displacement of the labile chloride of the allophanyl chloride withan oxime takes place preferably in an inert liquid reaction medium suchas, for example, benzene and toluene. A sequestering agent can bepresent to remove the hydrogen chloride and force the reaction tocompletion. Examples of such sequestering agents are tertiary aminessuch as, for example, triethylamine. The reaction temperature for thisstep is preferably between about 25° C. and about 80° C.

The oximinyl allophanate of this invention in general are viscousliquids at 20°-25° C., although some are crystalline solids at thistemperature. In general, the water-solubility of each is less than onegram per liter of water, the acetone-solubility of each is greater than5 grams per liter of acetone, and the benzene-solubility is greater than10 grams per liter of benzene.

In general, they are biologically active, being phytotoxic to plants,particularly weeds. Hence, they are useful as herbicides. For herbicidaluse, generally the oximinyl allophanates are incorporated intoherbicidal compositions.

The herbicidal compositions of this invention comprise an effectivequantity of phytotoxic material and application aid material.

The phytotoxic material comprises an oximinyl allophanate of thisinvention, a mixture of two or more of these oximinyl allophanates or amixture of at least one of these oximinyl allophanates and anotherphytotoxic substance.

The application aid material is inert material that facilitatesdistribution or dispersion of the phytotoxic material. Examples ofapplicaton aid material include diluents, carriers, extenders,surfactants, spreading agents, sticking agents, wind drift controlagents, and the like.

The oximinyl allophanates of this invention can be used in herbicidalcompositions dissolved or dispersed in a suitable liquid applicationaid. The liquid application aid is an inert preferably volatile solventfor the oximinyl allophanate. Water soluble oximinyl allophanates can bedissolved in water for herbicidal use. Water-insoluble oximinylallophanates can be dissolved in a suitable solvent, such as, forexample, isophorone, cyclohexanone, methyl isobutyl ketone, xylene, andthe like, to form herbicidal compositions. The solution of the oximinylallophanate in the solvent is initially in the form of a concentrate.The concentrate can be used directly as the herbicidal composition or itcan be diluted with additional solvent or it can be dispersed in water.

Solutions of the oximinyl allophanates dissolved in suitable solventsand oximinyl allophanates which are themselves liquid can also beimpregnated into an inert granular solid carrier to provide solidherbicidal compositions. Examples of the inert granular carrier includeattaclay, corn cobs, vermiculite, walnut hulls, and almost any granularmineral or organic material of desired particle size.

The solid oximinyl allophanates of this invention can be used inherbicidal compositions along with a finely divided inert solidapplication aid.

The solid oximinyl allophanates can be coated onto a granular inertcarrier which has been admixed with an adhesive or sticker, such as, forexample, water, oils, alcohols, glycols, aqueous gums, waxes, and thelike, to form a wettable powder or ground powder. Examples of inertgranular carriers include attaclay, corn cobs, vermiculite, walnut hullsand almost any other granular mineral or organic material of desiredparticle size.

The oximinyl allophanates of this invention can be employed according toother known methods of herbicidal application.

The best mode now contemplated of carrying out this invention isillustrated by the following working examples of various aspects of thisinvention, including specific embodiments. This invention is not limitedto these specific embodiments. In these examples, unless otherwiseexpressly indicated, all percentages are by weight, all parts by weightare represented by "w", all parts by volume are represented by "v" and wis to v as the kilogram is to the liter.

EXAMPLE 1

This example illustrates the preparaton of acetoneoximinyl-2-methyl-4-phenyl allophanate by reacting acetone oximinyl(N-methyl) carbamate with phenyl isocyanate.

A solution of 250 w of acetone oximinyl (N-methyl) carbamate, 2000 v ofdry benzene, 5.6 v of 24% lead naphthenate in mineral oil and 230 w ofphenyl isocyanate is heated at reflux for 6 hours. The solution is thencooled and concentrated. The residual solid is washed on a filter withice-cold ether and then thoroughly dried. Typically 227 w of a whitesolid having a melting point of 118° C. is obtained. Thin layerchromatography (using 90% benzene, 8% acetone, 2% isopropanol) of theproduct typically reveals a single spot, R_(f) 0.50. The nuclearresonance magnetic spectrum (CDCl₃) typically is δ 2.04 [d, 6, (CH₃)₂-C], 3.32 (s,3,N-CH₃), 7.0-7.7 (m,C₆ H₅ --), 8.34 (s,1,N-H). Massspectroscopy reveals a parent peak at m/e 249. [The calculated molecularweight of acetone oximinyl-2-methyl-4-phenyl allophante is 249.]

EXAMPLE 2

This example illustrates the preparation of acetoneoxime-2-methyl-4-phenyl allophanate by the reaction of 1-methyl-3-phenylurea with phosgene followed by the reaction of the resulting2-methyl-4-phenyl allophanyl chloride with acetone oxime.

A mixture of 145 w of 1-methyl-3-phenyl urea and 1000 v of dry benzeneis cooled to 10° C. A 12.5% phosgene in benzene solution is then addedslowly to the cooled mixture with stirring. The resulting mixture isstirred at ambient temperature for 1.5 hours than at reflux for 2.5hours. The mixture is cooled and the solids are removed by filtration. Asmall sample of the filtrate is removed, concentrated and then analyzedfor nitrogen content. The analysis typically shows N = 13.6. (Calculatedanalysis for 2-methyl-4-phenyl allophanyl chloride is N = 13.2%.)

The remainder of the filtrate solution is treated with 68.6 w of acetoneoxime. A solution of 95 w triethylamine and 100 v dry benzene is addedover a period of 75 minutes while the solution is stirred. Stirring iscontinued at room temperature for 2 hours and then at reflux for 1/2hour. The solution is cooled and the solids are filtered and washed with150 v benzene. The combined filtrate and wash are washed with two 300 vportions of 5% HCl, dried over magnesium sulfate and concentrated.Typically an orange solid residue is obtained, which when washed withice-cold ether and dried yields a white solid having a melting point of119°-121° C.

EXAMPLE 3

This example illustrates the preparation of isobutyraldoximinyl2-methyl-4-(3,4-dichlorophenyl)allophanate by the reaction ofisobutyraldoximinyl(N-methyl)carbamate with 3,4-dichlorophenylisocyanate.

A soluton of 5 w isobutyraldoximinyl (N-methyl) carbamate, 50 v drydioxane, 8 drops of lead naphthenate and 5.9 w of 3,4-dichlorophenylisocyanate is heated at reflux for 2 hours. The reaction mixture is thencooled and the solids are removed by filtration. The filtrate isconcentrated typically to produce an oily residue (6.1 w). The infraredspectrum of the residue typically has all the bands expected fromisobutyraldoximinyl 2-methyl-4-(3,4-dichlorophenyl)allophanate. Theanalysis for nitrogen content of the oily residue typically shows N =10.5 (calculated analysis for isobutyraldoximinyl2-methyl-4-(3,4-dichlorophenyl)allophanate = 12.6.)

EXAMPLE 4

This example illustrates the preparation ofisobutyraldoximinyl-2-methyl-4-(3,4-dichlorophenyl)allophanate by thereaction of 1-methyl-3-(3,4-dichlorophenyl) urea with phosgene followedby reaction of the resulting allophanyl chloride withisobutyraldoximine.

A mixture of 14 w 1-methyl-3-(3,4-dichlorophenyl) urea and 100 v drybenzene is cooled and stirred. A 12.5% phosgene in benzene solution isadded dropwise over a period of about 1 hour. The resultant mixture isstirred at 25°-30° C. for 18 hours then at reflux for 3 hours. Themixture is then cooled, solids are removed by filtration and thefiltrate is concentrated. Typically the residue comprises a tacky, whitesolid consisting essentially of2-methyl-4-(3,4-dichlorophenyl)allophanyl chloride.

8.5 w of the allophanyl chloride is stirred with 50 v dry benzene and2.61 w isobutyraldoxime. A solution of 3 w of triethylamine and 5 w ofdry benzene is added. The mixture is stirred at 25-30° C. for 1 hourthen at reflux for 1/2 hour. The mixture is cooled, the solids areremoved by filtration and then washed with dry benzene. The combinedfiltrate and wash are then washed with 5% HCl. The solids which areformed at this point are then removed by filtration. The organicfraction is dried and concentrated. Typically the residue comprises abrown resin which consists essentially ofisobutyraldoximinyl-2-methyl-4-(3,4-dichlorophenyl)allophanate (4.4 w).The residue is analyzed for nitrogen content. The analysis typicallyshows N = 11.5. (Calculated analysis, N = 12.6.)

The herbicidal activites of the oximinyl allophanates of this inventionare illustrated by actual test data summarized in Tables 1 and 2,obtained under standard test conditions with representative oximinylallophanates made according to the procedures of the foregoing examples.

In each case a concentrate was made from a sample of the oximinylallophanate by dissolving it in acetone and then adding a commerciallyavailable emulsifier which is a blend of a polyoxyethylene (20) sorbitanmonooleate in which the oxyethylene content is about 20 mole per cent,with mono- and di-glycerides of fat-forming fatty acids and anantioxidant mixture consisting essentially of butylated hydroxy anisol,butylated hydroxy toluene, citric acid and propylene glycol. The liquidconcentrate was then admixed with water to form an aqueous emulsion withthe allphanate at the desired concentration, and the resulting emulsionwas then applied in pre-emergence and post-emergence tests.

In the pre-emergence tests seeded pots with seeds of plants identifiedin Table 1 were sprayed uniformly under a spary of the emulsionsufficient to give a coverage of the allophanate at the indicated poundsper acre of allophanate under test. The extent of plant growth injurywas observed after a period of time sufficient for germination andgrowth of seed and compared to unsprayed seeded pots. The extent ofgrowth and injury was graded from no effect to no growth or completeinjury on a scale from 0 to 10.

For post-emergence tests the seeded pots were held under moist growingconditions until the seedlings had reached the first true leaf stage andthen the foliage was sprayed with emulsion sufficiently to give acoverage of the indicated pounds per acre of product under test. After aperiod of time sufficient for further growth, the extent of plant injuryand mortality was determined using the same grading system as above. Theresults are shown in Table 2.

The oximinyl allophanates of this invention exhibit higher herbicidalactivity than the corresponding oximinyl carbamates. The pre-emergenceand post-emergence herbicidal activities of certain oximinylallophanates and the corresponding oximinyl carbamates were determinedby the herbicidal test methods described above. Tables 3, 4 and 5 showthe comparison between these herbicidal activities.

Various features, advantages and specific embodiments of this inventionwill be readily apparent to those exercising ordinary skill in the artafter reading the foregoing disclosures. Such specific embodiments arewithin the scope of the claimed subject matter unless expressly indictedotherwise. Moreover, while specific embodiments of this invention havebeen described in considerable detail, variations and modifications ofthem can be effected without departing from the spirit and scope of theinvention as disclosed and claimed.

The terminology "consisting essentially of " as used in thespecification (disclosure and claims) excludes any unrecited substanceat a concentration sufficient to substantially adversely affect theessential properties and characteristics of the composition beingdefined, while permitting the presence of one or more unrecitedsubstances at concentrations insufficient to substantially adverselyaffect said essential properties and characteristics.

                                      TABLE 1                                     __________________________________________________________________________    PRE-EMERGENCE ACTIVITY                                                                        Rate                  Morn-  Vel-                                                                             Giant                                                                             Barn-                                     b./                                                                              Cot-   Soy-                                                                              Crab-                                                                             Mus-                                                                              ing    vet                                                                              Fox-                                                                              Yard                                                                              Pig-                                                                             Sor-               Compound        Acre                                                                             ton                                                                              Wheat                                                                             beans                                                                             grass                                                                             tard                                                                              Glory                                                                             Corn                                                                             Leaf                                                                             tail                                                                              Grass                                                                             weed                                                                             ghum               __________________________________________________________________________     ##STR6##       2 4                                                                              10 2 5 6 8 7 9 7 8 2 3 2 5                                                                               9 10                                                                            5 6 8 10                                                                              10 10                                                                            0 3                 ##STR7##       2 4                                                                              3 0                                                                              2 3 0 0 0 4 6 10                                                                              0 4 0 2                                                                               8 10                                                                            9 9 10  10 10                                                                            0 4                 ##STR8##       2 4                                                                              1  3                                                                             5 6 2 5 10  10                                                                            10  10                                                                            9 10                                                                              6  7                                                                             10 10                                                                            8 9 6 9 10 10                                                                            2 5                __________________________________________________________________________

                                      TABLE 2                                     __________________________________________________________________________    POST-EMERGENCE ACTIVITY                                                                          Rate         Barn-     Giant  Vel-   Wild                                                                             Morn-                                 lb./                                                                             Cot-                                                                             Sor-                                                                             Soy-                                                                              yard   Tea-                                                                             Fox-                                                                              Pig-                                                                             vet                                                                              Crab-                                                                             Mus-                                                                             ing                Compound           Acre                                                                             ton                                                                              ghum                                                                             beans                                                                             Grass                                                                             Corn                                                                             weed                                                                             tail                                                                              weed                                                                             Leaf                                                                             grass                                                                             tard                                                                             Glory              __________________________________________________________________________     ##STR9##          1 2                                                                              1 4                                                                              10 10                                                                            10 10                                                                             8 8 8 9                                                                               9 10                                                                            5 8 4 10                                                                             10 10                                                                             8 10                                                                             10 10                                                                            10 10               ##STR10##         1 2                                                                              10 10 10                                                                              10                                                                              10  10                                                                            8  10                                                                            10 10                                                                            8 9 10 10 10                                                                             10 10                                                                            10 10                                                                            10 10               ##STR11##         1 2                                                                              4 5                                                                              10 10                                                                            10 10                                                                             10  10                                                                            9 10                                                                              8 10                                                                            7 8 8 8                                                                              10 10                                                                            10 10                                                                             10 10                                                                            10 10               ##STR12##         1 2                                                                              10 10 10                                                                            10 10                                                                             10  10                                                                            9 9                                                                              10 10                                                                            9 10                                                                              6 10                                                                             10 10                                                                             9  9                                                                             10 10                                                                            10 10               ##STR13##         1 2                                                                              6 7                                                                               5  9  9                                                                             7 10                                                                              9 10                                                                              9 10                                                                            10  10                                                                            10  8 10 10                                                                              10 10                                                                           10 10               ##STR14##         1/2 1                                                                            2 3                                                                               3 10 10                                                                             8 9 10  3 15                                                                            10  10                                                                            10  3 10 10                                                                             10 10                                                                            10 10               ##STR15##         1/4 1/2                                                                          0 1                                                                               5  3  5                                                                             3 7 4 6                                                                               2 3 6 2 3                                                                               3  3  4                                                                              3  8 10               ##STR16##         1 2                                                                              5 7                                                                               8 10                                                                             6  8                                                                             5 6 6 9                                                                              10 6 7 5  6                                                                              5  9 10                                                                              8 10                                                                             9 10               ##STR17##         1 2                                                                              4 5                                                                               9 10                                                                             4  5                                                                             3 8 6 9                                                                               6 10                                                                            7 9 3 8                                                                               5 10                                                                            10 10                                                                              9 10                                                                             9 10               ##STR18##         1 2                                                                              4 5                                                                               8 10                                                                             7  7                                                                             4 5 7 9                                                                               8 9 10                                                                              4 6                                                                              10  9 10                                                                              9 10                                                                            10 10              __________________________________________________________________________

                                      TABLE 3                                     __________________________________________________________________________    PRE-EMERGENCE ACTIVITY COMPARISON                                                             Rate                                                          Compound        lbs./A                                                                            Millet                                                                            Corn                                                                             Mustard                                                                            Cotton                                                                            Soybean                                   __________________________________________________________________________    Acetone oximinyl 2-methyl-4-                                                                   2  6   5  10   4   8                                         phenyl allophanate                                                            Acetone oxime N-phenyl                                                                         2  7   2  10   5   0                                         carbamate                                                                     Isobutyraldoximinyl N-methyl                                                                   2  0   0   0   0   --                                        carbamate                                                                     Acetone oximinyl 2-methyl-4-                                                                  20  10  9  10   10  10                                        phenyl allophanate                                                            Acetone oxime N-phenyl                                                                        20  10  8  10   10  9                                         carbamate                                                                     Isobutyraldoximinyl N-methyl                                                                  20  0   0   4   0   --                                        carbamate                                                                     __________________________________________________________________________

    TABLE 4      POST-EMERGENCE ACTIVITY COMPARISON  Rate Al- Barn-    Cu- Giant Morn-              Wild   Com- lb./ fal- yard  Cot- Crab- cum- Fox- ing Mil-  Pig-           Velvet-  Mus- pound Acre fa grass Corn ton grass ber tail Glory     let Peas weed Sugarbeet Sorghum Soybeans Sunflower Teaweed Tomato leaf     Wheat tard Wild oats                        (1-      *  1 2  3 6 6 1 10 10 9  9 3 1 10 6 2 2 9     10) 10 10 5 10 6 ** 2 2 10 3 2 0  9  3 6  0 5 0  9 8 0 0 0  9   4  9 0     10 0 *  1 4 10 9 -- 3 10 10 9 10 6 2 10 8 5 5 9 10 10 10 6 10 7 ** 2 4     10 6 2 0  9  5 8 10 8 0 10 8 2 0 2 10  6 10 5 10 0 *  1 8 10 10  8 5 10     10 10  10 10  5 10 10  8 8 10  10 10 10 10  10 7 ** 2 8 10 9 3 0 10  8     10  10 9 1 10 10  1 9 6 10       * Acetone oximinyl 2-methyl-4-phenyl allophanate     ** Acetone oximinyl N-methyl carbamate

                                      TABLE 5                                     __________________________________________________________________________    POST-EMERGENCE ACTIVITY COMPARISON                                                             Rate                                                         Compound         lbs./A                                                                            Millet                                                                            Corn                                                                             Mustard                                                                            Cotton                                                                            Tomato                                                                            Marigold                             __________________________________________________________________________    Isobutyraldoximinyl                                                                             1  10  9  10   9   10  10                                   2-methyl-4-phenyl allophanate                                                 Acetone oximinyl N-methyl                                                                       1   0  0   0   0    0   0                                   carbamate                                                                     Isobutyraldoximinyl                                                                            10  10  10 10   10  10  10                                   2-methyl-4-phenyl allophanate                                                 Acetone oximinyl N-methyl                                                                      10   0  3   5   2    0   1                                   carbamate                                                                     __________________________________________________________________________

What I claim and desire to protect by Letters Patent is:
 1. A herbicidalcomposition comprising (1) application aid material and (2) an effectivequantity of phytotoxic material comprising a compound of the formula:##STR19## in which when R¹ and R² are taken separately, R¹ is selectedindependently from the group consisting of hydrogen and C₁ -C₇ alkyl andR² is selected independently from the group consisting of C₁ -C₇ alkyland phenyl, and, when taken together with the carbon atom to which theyare attached R¹ and R² form a C₃ -C₈ cycloalkyl group; R³ is selectedfrom the group consisting of C₁ -C₇ alkyl, allyl, phenyl, 3-halophenyland 3,4-dihalophenyl; and R⁴ is selected from the group consisting of C₁-C₇ alkyl; allyl, cyclohexyl, phenyl, halophenyl, tolyl, anisolyl,nitrophenyl, 3,4-dihalophenyl, 1-naphthyl, p-toluene sulfonyl,trihalomethylphenyl and 2,6-dinitro-4-trihalomethylphenyl.
 2. A methodfor the control of weeds which comprises applying to the soil aneffective quantity of material selected from the group of compounds ofthe formula: ##STR20## in which when R¹ and R² are taken separately, R¹is selected independently from the group consisting of hydrogen and C₁-C₇ alkyl and R² is selected independently from the group consisting ofC₁ -C₇ alkyl and phenyl, and, when taken together with the carbon atomto which they are attached R¹ and R² form a C₃ -C₈ cycloalkyl group; R³is selected from the group consisting of C₁ -C₇ alkyl, allyl, phenyl,3-halophenyl and 3,4-dihalophenyl; and R⁴ is selected from the groupconsisting of C₁ -C₇ alkyl, allyl, cyclohexyl, phenyl, halophenyl,tolyl, anisolyl, nitrophenyl, 3,4-dihalophenyl, 1-naphthyl, p-toluenesulfonyl, trihalomethylphenyl and 2,6-dinitro-4-trihalomethylphenyl. 3.The method according to claim 2 in which said material consistsessentially of a compound of said formula in which R¹, R² and R³ areeach methyl, and R⁴ is phenyl.
 4. The method according to claim 2 inwhich said material consists essentially of a compound of said formulain which R¹ is hydrogen, R² is isobutyl, R³ is methyl, and R⁴ is phenyl.5. The method according to claim 2 in which said material consistsessentially of a compound of said formula in which R¹ and R² togetherwith the carbon to which they are bonded form cyclohexyl, R³ is methyl,and R⁴ is phenyl.
 6. A method for the control of weeds which comprisesapplying to the foliage of said weeds an effective quantity of materialselected from the group of compounds of the formula: ##STR21## in whichwhen R¹ and R² are taken separately, R¹ is selected independently fromthe group consisting of hydrogen and C₁ -C₇ alkyl and R² is selectedindependently from the group consisting of C₁ -C₇ alkyl and phenyl, and,when taken together with the carbon atom to which they are attached R¹and R² form a C₃ -C₈ cycloalkyl group; R³ is selected from the groupconsisting of C₁ -C₇ alkyl, allyl, phenyl, 3-halophenyl and3,4-dihalophenyl; and R⁴ is selected from the group consisting of C₁ -C₇alkyl, allyl, cyclohexyl, phenyl, halophenyl, tolyl, anisolyl,nitrophenyl, 3,4-dihalophenyl, 1-naphthyl, p-toluene sulfonyl,trihalomethylphenyl and 2,6-dinitro-4-trihalomethylphenyl.
 7. The methodaccording to claim 6 in which said material consists essentially of acompound of said formula in which R¹, R² and R³ are each methyl, and R⁴is phenyl.
 8. The method according to claim 6 in which said materialconsists essentially of a compound of said formula in which R¹ ishydrogen, R² is isobutyl, R³ is methyl, and R⁴ is phenyl.
 9. The methodaccording to claim 6 in which said material consists essentially of acompound of said formula in which R¹, R² and R³ are each methyl, and R⁴is p-nitrophenyl.